Allylic sulfide reaction products

ABSTRACT

The present invention relates to novel low molecular weight addition products, cured mastic compositions formed from said products, and to pesticidal compositions containing said products. More particularly, the present invention is directed to low molecular weight addition products formed by the free radical addition of monothiols or dithiols to diallylic sulfide compounds and to vulcanizates and pesticidal compositions formed from said products.

United States Patent Oswald et al.

[111 3,859,360 [4 1' *Jan. 7, 1975 ALLYLlC SULFIDE REACTION PRODUCTS Inventors: Alexis A. Oswald, Mountainside;

Daniel N. Hall, Linden; Karl Griesbaum, Elizabeth, all of NJ.

Esso Research and Engineering Company, Linden, NJ.

Assignee:

Notice: 0 The portion of the term of this patent subsequent to July 13, I988, has been disclaimed.

Filed: Dec. 7, 1971 Appl. No.: 205,769

Related US. Application Data Division of Ser. No. 9,l26, Feb. 11, l970, Pat. No.

3,686,326, which is a continuation of Ser. No.

584,109, Oct. 4, 1966, abandoned.

US. Cl.... 260/609 D, 204/159.22, 204/159.23, 260/2 EC, 260/41 R, 260/45.95, 260/77.5

CR, 260/79, 260/79.5 C, 260/79.7,

Int. Cl; C08d 9/08 [58] Field of Search..... 260/79, 79.7, 609 B, 609 D,

[5 6] References Cited UNITED STATES PATENTS 3,403,187 9/l968 Oswald 260/609 3,503,940 3/l970 Oswald 260/79.7 3,592,798 7/1971 Oswald 260/79 3,717,618 2/1973 Oswald 260/887 Primary Examiner-Christopher A. Henderson 57 ABSTRACT tions formed from said products.

7 Claims, No Drawings cine-capitals sn ns-orn-o ALLYLIC SULFIDE REACTION PRODUCTS CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of application Ser. No. 9,126, filed Feb. 11, 1970, now US. Pat. No. 3,686,326, which in turn is a streamlined continuation of applicatiaon Ser. No. 584,109, filed Oct. 4, 1966, now abandoned.

The present invention relates to novel low molecular weight addition products, cured mastic compositions formed from said products, and to pesticidal compositions containing said products. More particularly, the present invention is directed to low molecular weight addition products formed by the free radical addition of monothiols or dithiols to diallylic sulfide compounds and to vulcanizates and pesticidal compositions formed from said products.

The reactionof thiol compounds (mercaptans), with diallylic compounds has been reported in the literature.

For example, Fr,iedlander in a present'ationbefore the Organic Chemistry Division of the American Chemical Society at the Spring, 1958, San Francisco meeting,

stated that onadding radical reagents, such as thiols, to materials such as diallyl sulfide, cyclization reactions of the following type take place:

' In contrast, it is stated in U.S. Pat'No. 3,075,8713 that some thiol compounds, namely dialkyldithiophosphoric acids, give the following simple ionic (Markovnikov Type) diadducts with diallyl sulfides:

The polyaddition of dithiols,(dimercaptans) to diolefinic compounds is a known method for polythioether synthesis (High Polymers, Volume XIII, Part III, Polyalkylenev Sulfides and Other Polythioethers, Ed. N.

Gaylord, lnterscience Publishers, New York, 1962,

Page 8). A series of papers of CS. Marvel and coworkers starting in 1938 provides most of the original information. Marvel and A. H. Markhart (J. Polymer Sci, 6,71 1 (1951) have reported their attemptsto use diallyl sulfide in such polyadditions but reported that diallyl sulfide was incapable of reaction with. simple aliphatic dithiols such as hexamethylene dithiol.

Now. in accordance with the present invention, it has been found that both simple aliphatic and aromatic monothiols as well as thiol acids readily react with diallyl' sulfide compounds in the presence of free radical catalysts to yield radical-type (anti-Markovnikov type) monoand diadducts as opposed to the .cyclic and simple ionic adducts of the prior art. Similarly, it has been found that attractive polythioethers h'aving number average molecular weights varying from 300 to 7000 can be formed by the free radical promoted addition of di-, thiols with diallyl sulfide compounds. The polythioethers formed can be readily cross-linked to vulcanizates having attractive high temperature properties.

In accordance with one embodiment of this invention, there is provided a radical type addition product having the general formula wherein R is selected from the group consisting of hydrogen and methyl; and m varies from 1 to 2, wherein (1) when m is 2, T and U are each selected from the group consisting of hydrogen radicals; unsubstituted monovalent alkyl radicals, unsubstituted monovalent aryl radicals; substituted monovalent alkyl radicals; substituted monovalent aryl radicals; said substituted and unsubstituted alkyl and aryl'radicals having from 1 to 50 carbon atoms; acetyl radicals; thioacetyl radicals; dialkyl substituted thiophosphoryl radicals; diaryl substituted thiophosphoryl radicals; dialkyl substituted phosphoryl radicals; and diaryl substituted phosphoryl radicals, the alkyl and aryl substituents of said alkyl and aryl substituted thiophosphoryl and phosphoryl radicals having from 1 to 16 carbon atoms; and (2) when m is 1, U is as previously'defmed and T is selected from the group consisting of allyl radicals and methallyl radicals.

The overall reactions contemplated by this invention may be represented by the following equations:

The product of equation I is the predominant reaction product formed when excess amount of allylic sulfide is reacted with a monothiol compound. The product of equation II is a diadduct of the reaction of an excess amount of monothiol compound with a diallylic sulfide compound. The product of equation III results from an equimolar reaction of a .dithiol compound with a diallylic sulfide'compound. The product of equation IV is the predominant product when an excess amount of dithiol compound is used in the reaction depicted. The product of equation V occurs when an excess amount of di allylic sulfide compound-is reacted with the dithiol material. I

The value ofn can vary over a wide range. Generally, n ranges between 1 and lOOQpreferably between 1 and Products finding the greatest utility as the base constituent for mastic compositions exhibit n values vary ing from about 2 to 50. The polymeric products of this invention (equations Ill-V) are essentially colorless liquids or low melting solids having number average molecular weights varying from 300 to 7000, preferably from 500 to5000.

The monothiol utilized as a starting material in the reaction has the general formula:

lent alkyl and aryl radicals; substituted monovalent alkyl and aryl radicals, particularly chlorine, hydroxy,

alkylthio, carboxy, and carboalkoxy substituted alkyl' and aryl radicals, the substituted and unsubstituted alkyl and aryl radicals having from 1 to 50, perferably ethylene,

. 3 2 to 30 carbon atoms; acetyl radicals; thioacetyl radicals; dialkyland diaryl substituted thiophosphoryl radicals and dialk-yl and diaryl substituted phosphoryl radimula: HSR"SH where R is a divalent organic radical having from 2 to 30 carbon atoms, particularly divalent hydrocarbon radicals, and divalent radicals containing either sulfur, oxygen, phosphorus or silicon in addition to hydrogen carbon atoms. Preferably, R" is (1) a C -C divalent alkylene radical, e.g., dimethylene, hexamethylene, etc.; (2) a C C divalent unsaturated alkylene radical such as 2-butene-l,4-ylene, 2-butyne- 1,4-ylene, etc.; (3) a C -C bis-alkylene substituted ar- R Desired Product omat'ic radical, e.g., p-xylylene,"p bis-dimethylenebenzene, etc.; ,(4) a C -C divalent aromatic radical such as m-phenylene, 1,5-naphthylen'e, etc.; and (5) a C C 5 divalent organic hydrocarbon radical containing either sulfur, phosphorus, oxygen or-silicon in .addition to carbon and hydrogen atoms such as thio-bisoxy-bis-ethylene, thio-bis-trimethylene, thio-bis-ethylthioethylene, di-methylsilane-bis-ethylene,

etc.

Particularly preferred thiols are those compounds whereRl' is a lower alkylene'radical having from 2 to 4 carbon atoms since such materials are especially reactive and yield polymeric substances of outstanding resistance to auto-oxidation and hydrocarbon solvents.

The diallylic sulfide compounds used for starting materials havegthe general formula donor ability-For example,.a smaller excess of a thiol,

product formed. Moreover, whether a monoadduct or a diadduct is formed from the reaction of a monothiol with a diallylicsulfide compound is determined by whether either excess sulfide or excess thiol is used in the reaction. When excess sulfide is used, the predominant product is a monoadduct, whereas when excess thiol compound is used, the predominant product is the diadduct of the diallylic sulfide compound. When monoadducts are the desired product, the molar ratio of allylic sulfide to monothiol should be maintained be-' tween about 111.2 to 01:1. When the diadduct is the desired product, the molar ratio ofallylic sulfide to monothiol should be maintained in the range between about 1:2 to 1:20.

The ratio of the allylic sulfide to the thiolic compound influences not only the proportion of the monoand the di- (or poly-) adduct formed-but also the formation of by-products. These by-products are formed by the following radical'cleavage processes:

l cleavage By-Product press by-product formation a smaller excess of the thiol compound is required if it has a high hydrogen atom acid is sufficient.

The molecular weight of polymeric products formed by the reaction of diallylic sulfides with, dithiols is strongly dependent upon the ratio of sulfide and dithiol present in the reaction zone. It has been found that unity, high molecular weight products are formed. It.

when the molar ratio of sulfide to dithiol is at or near was also found that the use of a large excess of either the dithiol compound or. the diallyl sulfide compound, in addition to effecting the final composition of the final polymer formed, serves to markedly reduce the ducts from diallyl sulfide compound and monothiols as well as the reactions for the formation of polymeric substances wherein dithiols were employed can be car- 'ried out in bulk, in the presence of inert diluents, or with the use of water emulsion techniques. The monoand diadducts of diallyl sulfide as well as low molecularweight polythioether compounds suitable as the base constituent in mastic compositions can beprepared most efficiently using bulk polymerization techniques, that is, carrying out the addition reaction in the absence of solvents. When higher molecular weight polythioether materials are desired, the addition reaction is preferablycarried out in the presence of an inertsolvent; however, high molecular weight materials can also be secured if the reaction is carried out in a typical water-surfactant emulsion system.

Useful inert solvents include saturated aliphatichydrocarbons, halogenated saturated aliphatic hydrocarbons,.aliphatic ethers, and aliphatic thioetherssuch as pentane, cyclohexane, dimethyl sulfide, trimethylene disulfide, etc. The use of aromatic hydrocarbons as solvents usually results in sharply reduced reaction rates and sometimes leads to undesirable side reactions.

sure within the reaction zone should be adjusted such that the diallylic sulfide and monothiol or dithiol reactantsare in the liquid state during reaction. For bulkaddition reactions, the temperatures varying from .-l to 175C, preferably 30 to 140C. can be used. When the compositions are formed in the presence of a solvent, temperatures varying from -30 to 140C., preferably 0 to 50C., are used. When emulsion techniques are utilized, the reaction should be conducted at temperatures varying from 0 to 50C.

The reaction contemplated by this invention-is not critically sensitive to pressure provided that the reaction pressure is sufficient to maintain the reactants in the liquid state at the temperatures of reaction. In general, pressures ranging from 0.5 to 10 atmospheres,

- preferably from 1 to 5 atmospheres, can be conveniently used. In most industrial applications, the pressure within the reaction zone will normally be the autogeneous pressures exerted by the reactants.

The reaction times used in the formation of either the monoor diadducts or the polymeric substances of this invention are not critical{ however, sufficient time should be allowed for the desired monomer conversion which depends upon temperature, reactant concentration, activity of catalyst used, etc. High yields of the adduct of polythioether products are secured within the temperature and pressure limits set forth above within 1 to 300 hours.

While not absolutely essential to the formation of the polythioether or monoor diadduct products, it is dethough pcroxidic initiators such as tbutylhydroperoxide, bis-t-butylperoxide, as well as materials such as bis-azobutyronitrile can also be used'. The chemical initiators are employed from 0.01 to 10 wt. concentration, based on reactants, preferably from 0.2 to 5 wt. concentration.

The reaction vessel utilized for the additionreactions can be constructed of any material that is inert to the reactants and catalyst used and is capable of withstanding the operating pressures. Reaction vessels constructed of stainless steel, and glass-lined steel are satisfactory.

The monoand diadducts of this invention formed by the reaction of diallylic sulfide compounds with monositions of this invention maybe employed in either solid or liquid form. When used in solid form, they may be ethanenedithiol and tetramethylenedithiol with an alreduced to animpalpable powder and employed as an undiluted dust, or they may be admixed with a solid carrier such as clay, talc, or bentonite as well as other carriers known to the art.

The compositions may also be applied as a spray, either alone or in a liquid carrier as a solution in a solvent or as a suspension in a nonsolvent. Useful solvents include organic compounds such as acetone, ethanol, benzene, naphtha, etc., although different compounds exhibit different solubilities for the present monoand diadduct compositions. in some instances, it may be preferable to mix the compositions, with wetting agents so as to be able to secure aqueous emulsions and consequent uniformity of dispersion in the resulting colloid system. The use of wetting agents also increases the wetting action of the spray by decreasing its surface tension. This results in securing better contact of the spray with the surface being treated and, consequently, brings the active ingredient into more intimate contact with the parasite'life. Suitable wetting agents include the sulfates of long-chained alcohols such as dodecanol and octa'clecanol, sulfonated amide or ester derivatives, sulfonated aromatic and mixed alkyl aryl derivatives, estersof fatty acids, such as the ricinoleic esters of sorbitol and petroleum sulfonates having from 10 to, 20 carbon atoms per molecule. The nonionic emulsifying agents such as ethylene oxide condensation products of alkylated phenols may also be employed. The compounds of this invention may, of course, be admixed with carriers that are themselves active insecticidal and miticidal compositions.

The adducts of monothiols such as dodecanethiol and hexadecyloxy ethanethiol and dithiols such as lylic sulfide are useful as oxidation stabilizers for hydrothe stabilizer is admixed with a major amount of the hydrocarbon product. For such applications. it is particularly advantageous to use the saturated dior poly adducts as c'ostabilizers in admixture with hindered phenols such as 2,6-di-t-butyl-4-methyl phenol. Such a I mixture shows a synergistic stabilizing effect for polymers formed from C to C alpha olefins such as polypropylene. Normally, up to 5 parts of the adduct is used per partsof hydrocarbon polymer.

The polymeric addition products of this invention have many uses as intermediates because of the thiol or I the total mixture at a temperature of from 80 to 150C. for a period ranging from 1 to hours. Similarly, the thiol terminated-products can be cured by admixing the polymer with an epoxide compound having at least 2 epoxide groupsper molecule and heating the resulting mixture inthe presence of an amine catalyst for a time sufficient to secure a cured network. Alternatively, these polymeric materials may be cured with diisocy-ahates to produce polythiourethanes. Due to their reactive thiol terminals,.they can also be reacted with allylic acrylates, divinyls'u lfone diacrylates and other reactive diolefinic compounds. They may also be cured by reaction with diepisulfides and the like.

Prior to curing or cross-linking operations, the polymeric addition products may be compounded with stabilizers, plasticizers or extender oils and various types of fillers; For example, carbon black," petroleum coke or mineral fillers may be incorporated into the polymer up to about parts, preferably up to 200parts, of

. pressure conditions yielded 21 grams (50% yield) of filler 'per 100 parts of' polymer. Amongthe carbon blacks that may be compounded with the polymeric addi tion products arethe channel blacks such as ETC, MPC, HPC etc., (these letters denoting carbon black productswell-known to the trade), the furnace blacks Fractional distillation of the mixture under reduced the diadduct having the structure CH S(CH S(CH SCH as a colorless liquid boiling at 1049-106C. at 5 mm. of mercury pressure. The radical-type adduct structure was shownby the n.m.r. spectrum of the isolated compound. The spectrum exhibited a 1:2 proton intensity ratio for methyl and methylene protons. The ionic'diadduct would have shown a 2:1 proton ratio, An'elemental analysis of the product also supported the assumed product structure. The calculated elemental analysis for C l-1 is C: 45.66, H: 8.62, S: 45.72. Found: C: 45.69;,1-1: 8.55; and S: 46.1.

EXAMPLE 2' A mixture of 76 grams (1 mole) of thiolace tic acid and 0.4 mole of diallyl sulfide was reacted in the manner described in the. previous example for 20 hours. Subsequent fractional distillationof the productin vacuo yielded 87 grams (82%) of a liquid diadduct fraction boiling between l40-l46C. at 0.1 mm. of

EXAMPLE 3 A mixture of 72 grams (0.5 mole) of 4- chlorobenzenethiol and 23v grams (0.2 mole) diallyl sulfide in i000 m1 n-heptane solvent was irradiated as described in Example l for 500 hours to'yield ally1,4'-

including- SRF, HAF, etc., and the thermal blacks, The 3 mineral fillerswhich maybe used include'any of the usual 'noncarbon black fillers or pigments such as the oxides, hydroxides, sulfides; carbonates and so forth of silicon, aluminum, magnesium, titanium, zinc or the like, or the silicates or aluminates of the various elements above indicated.

The cured mastic compositions of this invention are EXAMPLE 1 A stirred mixture of 26.5 grams (0.55 moles) of methanethiol and 22.8 grams (0.2 mole) of diallyl sulfide contained in a quartz pressuretube positioned within a water bath maintained at about 15C. wasirradiated with a 100 watt medium-pressure, wide wave length range, Hanau ultraviolet immersion lamp for 8 hours.

Following completion of reaction, the excess methanethiol was vented and the liquid residual product analyzed by a combination of vapor phase chromatography and proton magnetic resonance spectroscopy. The analysis indicated that the mixture was composed of about 75 mole 2,6,l0-trithio-undecane diadduct, 10 mole monoadduct, 10 mole dimethyl trimethylene-bis-sulfide cleavage product and 5% other materials. I

chlorophenyl sulfide, 3-(allylmercapto) propyl, 4- .chlorophenyl sulfide and bis-3-(4-chlorophenylmercapto)propyl sulfide, Y EXAMPLE 4 A stirred mixture of.-22.5 grams (0.21 mole) of distilled diethyldi-thiophosphoric acid and'l 1.4 grams (0.1 mole)" of diallyl sulfide contained in a quartz pressure vessel positioned within a water bath maintained at l5 C. was irradiated with a watt medium pressure, wide wave length range, Hanau ultraviolet immersion lamp. Samples of the reaction mixture were taken periodically during the course of the-reaction. Nuclear magnetic resonance'spectra of the reaction mixture indicated-that in 30 minutes, 50% of the diethyldithiophosphoric acid was chemically added to the diallyl sulfide. After 24 hours of irradiation, no more dithiophosphoric acid was left unreacted. The product formed was then solubilized in benzene and washed with a 5% aqueous sodium carbonate solution. Following the wasahing operation, the benzene was distilled from the mixture and the residue stripped at 60C.,under a nitrogen atmosphere at 0.7 mm. of mercury pressure to re move the un'reacted diallyl sulfide. The resulting residue was a clear, slightly yellow liquid product weighing 25 grams.

Analysis of the product using n.m.r. techniques indi cated the presence of about 60% mono'adduct and 40% diadduct. No branched, ionic type adducts we're present. A molecular weight determination by vapor pressure osmometry indicated a similar ratio of monoand diadduct. The calculated molecular weight for the monoadduct was 300 and for the diadduct 487. The deter- EXAMPLE Following the procedure of Example 4, a mixture of EXAMPLES A mixture of 135 grams (1.25 moles) of trime- -thy1enedithiol and 143 grams (1.25 moles) of diallyl 46 grams (0.25 mole) of diethyldithiophosphoric acid 5 Sulfide charged into a l f {fraction Vessel which and 11.4 grams (0.1 mole) of diallyl sulfide was reacted was l m Wlth a magnetlc $t1rrer a a nitrogm and subsequently u ifi d to yield 39 grams f a yellow bubbler. The reaction vessel was positioned within a li id product N le a i resonance spectra thermostating water bath maintained at C. The reanalysis of the product indicated that it was a mixture actams were irradiated Withconstant Stirring of about 86% of the radical type dia d 13% f h d- 10 under a nitrogen atmosphere with a 75 watt I-Ianau high ical type monoadduct, i.e. [(C H O) P(S)S(CH pressure mercury immersion lamp for 24 hours. At the and (C H O) P(S)S(CI-{ SCH CH=CH Thi c l completion of the reaction period, the originally color sion was supported by the following analysis: the calculess liquid product turned into a white semi-solid. Ex.- 1ated mol cular w i ht for diadd t; 437; th d t amination of samples taken from the reacting mixture mined molecular weight for the product obtained was 15 at vari us tim int r y nu l ar magn tic'reso- 438. The calculated elemental analysis for the diadnance spectroscopy showed'that this apparent change duct, C H O P S was C: 34.55; H: 6.62; O: 13.15; P: in physical state was preceded by a gradual decrease of 12.13; and S1 32.95 The elemental analysis of the allylic groups present in the reaction zone to about oneproduct revealed the following: C: 34.85; H: 6.55; O: fifth of the original value after 24 hours. 13.0; P 12.53 and S: 33.0. The crude reaction mixture recovered. was then dis- EXAMPLE 6 solved in 560 ml of benzene and the resulting solution Sam 0.1 mm of e. roducts of Exam leg 4 added dropwise to 2 500 ml of chilled methanol which and 5 aereldissoglved in 2 m] O acetone and disgersed caused the precipitation of the solid polymer. The solid in 200 ml ofdis'tilled water with 0.1 m1 of a Triton R P emered the t i X400 emulsifien In one test some of the resulting tion filtration and the material washed with additional 0.05% aqueous emsulsions were used to spray lima cold methanolalnddned m p' A 73% yleldouu bean leaves on the dorsal and ventral surfaces. These grams) of purified polymer memng. between and leaves were then offered for a 48 hour feeding period 58 C. was obtained. Nuclear magnettc resonance specto ten larvae of the Mexican Bean Beetle. In another 0 Ofthe pmduct showed the two types of Char test lima bean plants were infested with 50 to 100 aclenstw methylene g for h .mmet.hylene' adults of the Strawberry spider mite Tetranychus thioether repeating units in a 1:2 relative intensity. The lanticus, and then dipped into the test emulsions. analysls s mdlcated m p of Mortality determinations up to 48 hours showed that mately equal numbers of allyl and tho] F all the Mexican Bean Beetles were killed by both Suggests that h polymer was an alpha'auyl'omega" sprays. In the case of the spider mites, the predomime,rcaptopolymmethylenesulfide' The molecular nantly monoadduct product of Example 4 showed 89% of the polymer, was found to be 1845 deter mortality, the predominantly diadduct product of Exmmed by benzene ample 5 showed 88% mortality after 5 days. The beemolecular we'ght 9 the polymer formfid was tles and mites on theleaves treated only with water and 40 that Increase? P reactmg the polymer, wlth l f. emulsifier Show no mortality amounts of'dithrol compounds such as trimethylenedlv thiol thereby converting the terminal allyl functionality EXAMPLE 7 on the original polymer to thiol termination. In similar In another series of experiments, the products defashion, the terminal functionality of thiol terminated scribed in Examples l-4, were tested against fli'es, polythioethers was modified by reacting the'polymer roaches, fungi and nematodes. The results of these with an unsaturated alcohol such as allyl alcohol. Additests, as shown in the Table, indicate that'the products tionally, the polymer structure can be modified by reof the present invention have a wide spectrum pesticiacting a thiol terminated polythioether with a didal activity functionalreagentsuchas ethylenediacrylate.

TABLE I Control of Pest at a given Concentration of Product Product sullen-"e House Flies Roaches Product Cone. at Pest Control, L 50. from of Product Pest I Prod. Pest Con.,% Alternaria Monilia v Panagrellus Example Product a I 1 Cone. Conn-01% onc.% Male Female Solam Fructicola Nematode 1 [CH=S(CH1)slS 2.5 30 1.0 100 '60 0.01 0.01 0.001 2 [CH,COS(CH S v 2.5 1.0 60 0.001 0.001 0.0l 4 [(C,H O),P(S)S(CH,);,] S"" 2.5 2.5 100 80 0.01 0.01 0.001

. 0.1 47 5 (C H O),P(S)S(CH );SCH CE=CH 2.5 100 2.5 100 I00 0.0l 0.001 0.001

" bis (diethyl thiophosphoryl-mercaptopropyl) sulfide Q,O-diclhyl-S-allylmercaptopropyl dithiophnsphare EXAMPLE 9 The polyadduct of Example 8 and the reaction products resulting from'its conversion with trimethylenedio-.

thiol and allyl alcohol were examined by thermogravimetric analyses. Samples of the three polymers were heated at a temperature rise of 6C. per minute in both a nitrogen atmosphere and air. Temperatures were re corded as the polymers lost 1, 10, 50, 90 and 95 percent of their weight. The data obtained are tabulated in Table 11 below. i l

The tabulation shows that all three polymers are sta- 1 ble below 250C. It should be noted that the stability of the polymers on heating is almostthe same in air as it is in a nitrogen atmosphere. This points to an outstanding resistance towards autoxidation. It is believed that I the thio'ether sulfur of these polymers is'an effective antioxidant for the relatively short aliphatic hydrocarbon segments present in the polymer.

TABLE II lowed to cool to ambient temperature, where it solidified. The crude product was added to 500ml. of stirred pentane in which it partly dissolved. The undissolved part 15 grams) was recrystallized from 600 ml. of a 1 :1 mixture of benzene and heptane to yield 9 grams of white, powder-like solid of 1280 molecular weight as determined by vapor pressure osmometry. The powder product was believed to have the general formula: HS I( 2)10 2)3 2)3 ]1il( 2)10 2)3 I H CH==CI-I Polymer Structure Atmosphere Temperature of Per Cent Weight Loss- CH. ,=CIHCHZ(SCH,CHZC H2Y),ISH Nitrogen 255 326 350. 364 R I Air 247 314 336 3.44 345 HSCH,CH CH (SCH CH CI-I ),.SH Nitrogen' 291 33s 354 362 367 Air 275 318 335 345 1 R HOCI-l CI-hCH,(SCH CH CH ),,SCH CH Nitrogen -250 331 355 365 368 CH on I 2 Air 24s 318 341- 349 350 EXAMPLE l0 The calculated elemental analysis for (Ci l-l s is C: Follow rd-cedure of Exam 1E8 to 0'2 59. 94; I-I: 10.06; $230.00. The determined. elemental g p p 35 analysis was c; 60.50; H: 9.95; s;- 30.44.--

mole of various types ofpurified dithiols were reacted with equimolar amounts of distilled diallyl sulfide (boilingpoint 76 to 77C. at 109 mm. of mercury). Upon completion of the reaction, the crude products were heated at'temperatures varying-from 50 to' 100C. at

pressures ranging from 1.0 to 0.5 mm. of mercury for 24 hours -to remove starting materials. The resulting residue was'then dissolved in benzene and added dropwise to 5 volumes of stirred chilled methanol. The re- From the pentane' extract, oncooling to 1,5C., 1 2

grams of a waxy, white solid was obtained. The molecular weight of this latter product faction was 660 as determined by vapor pressure osmometry.

. EXAMPLE 12 A stirred, nitrogenated mixture of 28.5 grams (0.25 mole) of diallyl sulfide and 36 grams (0.3 mole) of tetrarnethylenedithiol was irradiated with the lamp of Example 1 for 96 hours at 16C. The resulting crude product was heated with nitrogen bubbling at 140C. for 2% hours to remove the volatiles. As a distillation residue, 58 grams (90%) of a' colorless liquid product was ob- TABLE III 1 U.V. v Chemical Irradiation, Crude Ebullioscopic Elemental Analysis, Run .Dithiol Reagent Initiator Hrs. Yield,% Mol. Wt. C H S 1 p-Xylylene Dimercaptan (CH COOH" 9 88 851 I 2- Ethylene Dimercapto Acetate (CHQ CQOI-IW- 48 56 749 V, 41.07 5.73 29.68 3 1,2-Propane Dithiol None 48 67- 827 49.38 8.09 42.91 4 p-Menthane Dithiol None 79 478 60.11 9.40 39.35 5 p-Xylylene Dimercaptan None" 48 50 860 6 Ethane Dithiol None 48 50 .603

"" cc benzene solvent P 10 cc benzene solvent The data set-forth in Table 111 above indicates that various types of low molecular weight polythioether ad.-

dition products can be formed by the free radical addition reaction of aliphatic andaromatic dithiols with diallylsulfide.

tained. Its osmotic molecular weight was found to be ;559. The .calculated molecular weight for the trimer having the general formula I( 2)4 2):3S( 2)a Ia( 2)4 2)a 2-- CI-I=CI-I 7 V i (n=3) is 536. The product was found to have the expected thiol functionality of one by titration with methyl maganesium bromide.

The calculated elemental analysis for [C H S is C: 50.80; H, 8.52; 5: 40.68. The determined elemental analysis was C: 50.77; H: 8.39; S: 41.44.

EXAMPLE 13 A stirred and nitrogenated mixture of 54 grams (0.5 mole) trimethylene dithiol and 71 grams (0.5 mole) di- (B-methallyl) sulfide was irradiated wiith ultraviolet light at 16C. for 96 hours. During the reaction period the mixture gradually turned orange-brown. However,

camscngpnongs-cmo-cm The calculated elemental analysis for [C H S I is C: 52.75; H: 8.85; S: 38.40. The elemental analysis of the product was C: 53.38; H: 8.94; S: 37.39.

EXAMPLE 14' A stirred mixture of 25.6 grams (0.18 mole) di-(B- methallyl) sulfide and 54 grams (0.5 mole) trimethylenedithiol was reacted at 16C. for 21 hours under the effect of ultraviolet irradiation. The resulting brownish-orange product was heated under nitrogen at 145C. under 0.15 mm. to remove all the volatile components. This resulted in 54 grams of a colorless, slightly viscous product. An n.m.r. spectrum of the product showed only a trace of unsaturation. Determination of molecular weight by the osmotic method in benzene solution gave a value of 475. The calculated value for the diadduct (n=1) and the triadduct (n=2) is 358 and 608, respectively.

It is to be understood that this invention is not limited to the specific examples which have been offered merely as illustrations and that modifications may be made without departing from the spirit of the invention.

What is claimed is:

1-. A polymeric radical type addition product having the general formula wherein R is selected from the group consisting of hydrogen and methyl radicals, R" is selected. from the group consisting of C to C divalent alkylene radicals, C to C divalent unsaturated alkylene radicals, C to C bis-alkylene substituted aromatic radicals, C to C divalent aromatic radicals, and C to C divalent organic hydrocarbon'radicals containing an element selected from the group consisting of sulfur, phosphorus, oxygen, and silicon in addition to carbon and hydrogen atoms and n varies from 2 to 50.

2. The product of claim 1 wherein R is methyl.

3. The product of claim 1 wherein R" is a lower alkylene radical having from 2 to 4 carbon atoms and n varies from 2 to 50.

4. The product of claim 1 wherein the product has a 0 number average molecular weight of 300-7000.

. 5. The product of claim 1 wherein the product has a number average molecular weight of 500-5000.

6. The product of claim 1 wherein R" is selected from the group consisting of 2-butene-l,4-ylene, 2- butyne-1,4-ylene, p-xylylene, p-bis-dimethylenebenzene and m-phenylene. p

7. The product of claim 1 wherein R" is thio bisethylene, oxy-bis-ethylene, thio-bis-trimethylene, thio-bis-ethylthioethylene V or dimethylsilane-bisethylene. 

1. A POLYMERIC RADICAL TYPE ADDITION PRODUCT HAVING THE GENERAL FORMULA
 2. The product of claim 1 wherein R is methyl.
 3. The product of claim 1 wherein R'''' is a lower alkylene radical having from 2 to 4 carbon atoms and n varies from 2 to
 50. 4. The product of claim 1 wherein the product has a number average molecular weight of 300-7000.
 5. The product of claim 1 wherein the product has a number average molecular weight of 500-5000.
 6. The product of claim 1 wherein R'''' is selected from the group consisting of 2-butene-1,4-ylene, 2-butyne-1,4-ylene, p-xylylene, p-bis-dimethylene-benzene and m-phenylene.
 7. The product of claim 1 wherein R'''' is thio-bis-ethylene, oxy-bis-ethylene, thio-bis-trimethylene, thio-bis-ethylthioethylene or dimethylsilane-bis-ethylene. 